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Title

Lanthanide-to-Lanthanide Energy-Transfer Processes Operating in Discrete Polynuclear Complexes: Can Trivalent Europium Be Used as a Local Structural Probe?

Authors
Eliseeva, Svetlana V.
Petoud, Stéphane
Published in Chemistry - A European Journal. 2014, vol. 20, no. 38, p. 12172-12182
Abstract This work, based on the synthesis and analysis of chemical compounds, describes a kinetic approach for identifying intramolecular intermetallic energy-transfer processes operating in discrete polynuclear lanthanide complexes, with a special emphasis on europium-containing entities. When all coordination sites are identical in a (supra)molecular complex, only heterometallic communications are experimentally accessible and a Tb[RIGHTWARDS ARROW]Eu energy transfer could be evidenced in [TbEu(L5)(hfac)6] (hfac=hexafluoroacetylacetonate), in which the intermetallic separation amounts to 12.6 Å. In the presence of different coordination sites, as found in the trinuclear complex [Eu3(L2)(hfac)9], homometallic communication can be induced by selective laser excitation and monitored with the help of high-resolution emission spectroscopy. The narrow and non-degenerated character of the Eu(5D0[LEFT RIGHT ARROW]7F0) transition excludes significant spectral overlap between donor and acceptor europium cations. Intramolecular energy-transfer processes in discrete polynuclear europium complexes are therefore limited to short distances, in agreement with the Fermi golden rule and with the kinetic data collected for [Eu3(L2)(hfac)9] in the solid state and in solution. Consequently, trivalent europium can be considered as a valuable local structural probe in discrete polynuclear complexes displaying intermetallic separation in the sub-nanometric domain, a useful property for probing lanthanido-polymers.
Keywords Energy transferLanthanidesPhotophysicsPolynuclear complexesStructural probes
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Other version: http://doi.wiley.com/10.1002/chem.201403206
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ZAIM, Amir Hossein et al. Lanthanide-to-Lanthanide Energy-Transfer Processes Operating in Discrete Polynuclear Complexes: Can Trivalent Europium Be Used as a Local Structural Probe?. In: Chemistry - A European Journal, 2014, vol. 20, n° 38, p. 12172-12182. https://archive-ouverte.unige.ch/unige:40570

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Deposited on : 2014-09-29

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